JPH03112803A - Novel crystalline aluminum phosphate and its related compounds - Google Patents
Novel crystalline aluminum phosphate and its related compoundsInfo
- Publication number
- JPH03112803A JPH03112803A JP2241346A JP24134690A JPH03112803A JP H03112803 A JPH03112803 A JP H03112803A JP 2241346 A JP2241346 A JP 2241346A JP 24134690 A JP24134690 A JP 24134690A JP H03112803 A JPH03112803 A JP H03112803A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum phosphate
- bipyridyl
- related compounds
- source
- crystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 55
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims description 33
- 239000000203 mixture Substances 0.000 claims abstract description 29
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 9
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- XLXJSJOICYRXSE-UHFFFAOYSA-N 2-pyridin-2-ylpyridine Chemical group N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 XLXJSJOICYRXSE-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 4
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- -1 t-butyramine Chemical compound 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JTBKFHQUYVNHSR-UHFFFAOYSA-N propan-2-yloxyalumane Chemical compound CC(C)O[AlH2] JTBKFHQUYVNHSR-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/04—Aluminophosphates [APO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【発明の詳細な説明】
皮呈上坐１１公！
本発明は新規な結晶性リン酸アルミニウム組成物および
かかるリン酸アルミニウムの製造法に関する。[Detailed Description of the Invention] The 11th Lord of the Skin Presentation! The present invention relates to novel crystalline aluminum phosphate compositions and methods for producing such aluminum phosphates.
盗】凶ｉ避
結晶性リン酸アルミニウム組成物は公知物質であり分子
篩、触媒担体及び触媒の新しい分野として工業上注目さ
れている０例えば米国特許第４３１０４４０号には種々
の結晶性リン酸アルミニウムが、とりわけ、水酸化テト
ラプロピルアンモニウム、キヌクリジン、ｔ−ブチラミ
ンおよびエチレンジアミン等を包含する有機構造管理剤
または有機構造型供与剤（ｔｅｍｐｌａｔｉｎｇ ａｇ
ｅｎｔ）を含む反応混合物から製造することを記載して
いる。[Theft] Crystalline aluminum phosphate compositions are well-known substances and are attracting industrial attention as new fields of molecular sieves, catalyst supports, and catalysts.For example, US Pat. No. 4,310,440 discloses various crystalline aluminum phosphate compositions. organic structure-directing agents or templating agents, including tetrapropylammonium hydroxide, quinuclidine, t-butyramine, and ethylenediamine, among others.
ENT).
これらの物質の組はＡｆＰＯ４，５ＡＰＯ４（シリコア
ルミノフォスフェート）、ＭｅＡＰＯ４（メタロアルミ
ノフォスフェート）およびＥｆＡＰＯ。These sets of materials are AfPO4,5APO4 (silicoaluminophosphate), MeAPO4 (metalloaluminophosphate) and EfAPO.
（非金属置換アルミノフォスフェート）族において結晶
した組成物を含む。(Non-metal-substituted aluminophosphates).
の
新規な結晶性リン酸アルミニウムおよびその関連化合物
、例えばＡｆｆｉＰＯ４−１Ｓ Ａ Ｐ Ｏａ−および
Ｍ ｅ Ａ Ｐ ０４−型の化合物が、適当な形成成分
と２．２′−ビピリジル化合物を使用する場合にその反
応ゲルまたは溶液から製造できることが発見された。new crystalline aluminum phosphates and related compounds, such as compounds of the AffiPO4-1S A P Oa- and M e A P 04- types, when using suitable forming components and 2,2'-bipyridyl compounds. It has been discovered that it can be prepared from the reaction gel or solution.
本発明はか（して合成無水形として化学組成ｍＲ（Ｘ、
ＡＪ！、Ｐ、）Ｏｓであって、ここにＲは２１２′−ビ
ピリジル（ビピリジン）部分であり、ＸはＡ１および／
またはＰに代替できるｌまたはそれ以上の元素を表し、
ｍ＝ｏ、０］＝０．３３、
ｎ−０＝０．４０、
ｑ＝０．３０＝０．６０、
Ｘ３０．３０−０．６０および
ｎ＋ｑ＋ｘ＝１である組成を有し、そして少なくとも下
記の分析線を含有するＸ線回折バタンを有する結晶性リ
ン酸アルミニウムおよび関連化合物に関する：
ｌ上
特に発明は好ましくは上記化学組成を有する結晶性リン
酸アルミニウムおよびその関連化合物において、
ｍ＝０．１０＝０．２０、
ｎ−０＝０．３０、
ｑ〜０．４４−０．６０および
ｘ＝０．４４＝０．６０であり更にｎ＋ｑ＋ｘ雪１であ
る化合物に関する。The present invention has the chemical composition mR(X,
AJ! , P, ) Os, where R is a 212'-bipyridyl (bipyridine) moiety and X is A1 and/
Or represents l or more elements that can be substituted for P, m=o, 0]=0.33, n-0=0.40, q=0.30=0.60, X30.30-0.60 and n+q+x=1 and having an X-ray diffraction pattern containing at least the following analytical lines: In aluminum phosphate and related compounds, m=0.10=0.20, n-0=0.30, q~0.44-0.60 and x=0.44=0.60, and n+q+x Regarding the compound that is Snow 1.
本発明に従う結晶性化合物中に存在するに特に好ましい
ものは１またはそれ以上のアルキル基、特に炭素原子６
個より多くないアルキル基、より特定的にはメチル、エ
チルおよび／またはプロピルを表すアルキル基を含有す
る２、２′−ビピリジル部分から誘導される化合物であ
る。Particularly preferred for presence in the crystalline compounds according to the invention are one or more alkyl groups, especially 6 carbon atoms.
It is a compound derived from a 2,2'-bipyridyl moiety containing not more than one alkyl group, more particularly an alkyl group representing methyl, ethyl and/or propyl.
特に好ましいものは２個の同様に置換したピリジル基か
ら構成される２、２′−ビピリジル部分から誘導された
化合物、より特定的には４．４′−ジメチル２．２′−
ビピリジルまたは２，２′−ビピリジルから誘導される
化合物である。Particularly preferred are compounds derived from a 2,2'-bipyridyl moiety composed of two similarly substituted pyridyl groups, more particularly 4,4'-dimethyl2,2'-
It is a compound derived from bipyridyl or 2,2'-bipyridyl.
本発明に従う結晶性リン酸アルミニウムおよびその関連
化合物中のアルミニウムおよび／またはリンと置換でき
る元素Ｘとして１またはそれ以上のベリリウム、マグネ
シウム、チタン、マンガン、鉄、コバルト、亜鉛、バナ
ジウム、ニッケル、クローム、ケイ素、リチウム、ホウ
素、ガリウム、ゲルマニウムおよび砒素を表し、好まし
くは１またはそれ以上のマグネシウム、マンガン、チタ
ン、鉄、コバルトおよびケイ素が適切に使用できる。As the element X which can replace aluminum and/or phosphorus in the crystalline aluminum phosphate and related compounds according to the invention, one or more beryllium, magnesium, titanium, manganese, iron, cobalt, zinc, vanadium, nickel, chromium, Silicon, lithium, boron, gallium, germanium and arsenic are represented, preferably one or more of magnesium, manganese, titanium, iron, cobalt and silicon can be suitably used.
ｎ〉０の場合は、合成無水形は更にプロトンまたはＲに
基づいた化合物のプロトン化形のような適当な電荷平衡
陽イオン（ｃｈａｒｇｅ−ｂａｌａｎｃｉｎｇ ｃａｔ
ｔｏｎ）をも含むことが判るであろう。If n>0, the synthetic anhydrous form is further conjugated with a suitable charge-balancing cation such as a proton or a protonated form of the R-based compound.
ton).
本発明に従うＡ Ｉ Ｐ Ｏ４の組に属する新規なリン
酸アルミニウムの例はその合成形において下記化学組成
を有する：
０．１３Ｒ（ＡＩ！、。、ｓＰａ、５）Ｏｚ、これは後
記表２に与えられる分析線を少なくとも含むＸ線回折パ
タンを有する（ここにＲは２．２′−ビピリジルから誘
導された化合物を表す）。An example of a novel aluminum phosphate belonging to the group A I P O4 according to the invention has the following chemical composition in its synthetic form: 0.13 R (AI!,., sPa, 5) Oz, which is shown in Table 2 below. (where R represents a compound derived from 2,2'-bipyridyl).
本発明に従いそしてＳ Ａ Ｐ Ｏａの組に属する新規
な結晶性リン酸アルミニウムの他の例としてはその合成
形において下記化学組成を有する：０、１２ Ｒ（Ｓ
ｉ ＊、＊、Ａｌｍ、ａａＰ＊、ａａ）Ｏｓ 、これは
後記表２に与えられる分析線を少なくとも含むＸ線回折
パタンを有する。Another example of a novel crystalline aluminum phosphate according to the invention and belonging to the group S A P Oa has the following chemical composition in its synthetic form: 0,12 R(S
i*,*,Alm,aaP*,aa)Os, which has an X-ray diffraction pattern that includes at least the analytical lines given in Table 2 below.
本発明に従いそしてＣｏ Ａ ｊ！ Ｐ Ｏａの組に属
する新規な結晶性リン酸アルミニウムの更に例とすると
ころはその合成形において、下記化学組成を有する：
０．１２Ｒ（Ｃｏ・、・４Ａｊ！ｏ、４ｙＰｅ、４．）
Ｏｔ １ これは後記表２に与えられる分析線を少なく
とも含むＸ線回折パタンを有する。According to the invention and Co A j! A further example of a novel crystalline aluminum phosphate belonging to the P Oa family, in its synthetic form, has the following chemical composition: 0.12R(Co...4Aj!o,4yPe,4.)
Ot 1 This has an X-ray diffraction pattern that includes at least the analytical lines given in Table 2 below.
本明細書に引用される無水形は更に場合によっては化学
的に結合した水を含みうろことは理解されるべきである
。It is to be understood that the anhydrous forms referred to herein may also optionally contain chemically bound water.
本発明は更に新規な結晶性リン酸アルミニウムおよびそ
の関連化合物であって下記一般化学組成を有する方塊さ
れたＲを欠除した形にも関する：（ＸａＡｊ！＊Ｐ−）
Ｏｇ−ここにＸ、ｎ、ｑおよびＸは前記と同様な意味を
有しそしてｎ＋ｑ＋ｘ＝１である。The invention further relates to novel crystalline aluminum phosphate and related compounds having the following general chemical composition: (XaAj!*P-)
Og-where X, n, q and X have the same meanings as above and n+q+x=1.
本発明は更に前記に記載の新規な結晶性リン酸アルミニ
ウムおよびその関連化合物を、アルミニウム源、リン源
、任意的には少なくとも一個のＸ成分給源および２．２
′−ビピリジル部分に基づいた型給源を含む生成溶液ま
たはゲルから製造する方法において、この混合物を結晶
性リン酸アルミニウムまたはその関連化合物を生成する
に充分な時間上昇温度で保ち、次いで得られた結晶性生
成物を分離し乾燥する方法であって、上記溶液またはゲ
ル内で上記種々の成分が当初から下記のモル比で存在す
る方法にも関する；
Ｒ：Ａｊ！ｇｏｓ＝０．１３
Ｘ ： Ａｊ！、０３３０−２
Ｐ ： ＡｌＯｓ ＝０．３−１，３
Ｈ２Ｏ： Ａｊ！＊Ｏｓ ＝−４０−５００本発明に従
う結晶性リン酸アルミニウムおよびその関連化合物は好
ましくは下記モル比で種々の成分が当初から存在する生
成溶液またはゲルから好ましく製造される：
Ｒ：Ａｌｇｏ、＝０．１５−２
Ｘ：Ａｆｆｉ□Ｏ，−０−２
Ｐ ： Ａ１．ｔｏｓ ”０．４ １．２５Ｈ２Ｏ
： Ａｌｇｏ、＝４５−３２０
前記合成無水形において前記表１に与えた分析線を少な
くとも含むＸ線回折パタンを有する結晶性リン酸アルミ
ニウムおよびその関連化合物は適切には８０°Ｃと２２
０°Ｃ間の温度を保つことにより、特に１００°Ｃ乃至
２００°Ｃの範囲内の温度で製造される。The present invention further provides the above-described novel crystalline aluminum phosphate and related compounds comprising an aluminum source, a phosphorus source, optionally at least one X component source and 2.2
In a process from a product solution or gel containing a type source based on the '-bipyridyl moiety, the mixture is held at an elevated temperature for a sufficient period of time to form crystalline aluminum phosphate or related compounds, and the resulting crystals are then R: Aj! gos=0.13 X: Aj! , 0330-2 P: AlOs =0.3-1,3 H2O: Aj! *Os = -40-500 Crystalline aluminum phosphate and its related compounds according to the invention are preferably prepared from a product solution or gel in which the various components are initially present, preferably in the following molar ratios: R:Algo, =0 .15-2 X: Affi□O, -0-2 P: A1. tos ”0.4 1.25H2O
: Algo, =45-320 The crystalline aluminum phosphate and related compounds having an X-ray diffraction pattern including at least the analytical lines given in Table 1 above in the synthetic anhydrous form are suitably heated at 80°C and 22°C.
By keeping the temperature between 0°C, in particular in the range 100°C to 200°C.
水性の生成溶液またはゲルの使用が好ましい。Preference is given to using aqueous product solutions or gels.
この生成溶液またはゲルの製造のため、２．２′−ビピ
リジル（ビピリジン）部分に基づいた給源または促進剤
形が型供給源として使用でき、例えば２，２′−ビピリ
ジル部分のような第４級化合物であり、この供給源また
は促進剤形は２．２′ビピリジル部分へと変換できるも
のでなければならない。For the preparation of this product solution or gel, a source or accelerating dosage form based on the 2,2'-bipyridyl (bipyridine) moiety can be used as a mold source, e.g. The source or promoter must be able to convert the compound into a 2,2' bipyridyl moiety.
本発明に従う方法は自然発生圧並びに上昇圧で実施でき
る０通常は本結晶性リン酸アルミニウムおよびその関連
化合物は、その生成溶液またはゲルを一定時間上記適当
な条件下に保って、その適切な構造を形成させることに
より製造されよう。The process according to the invention can be carried out at naturally occurring pressures as well as at elevated pressures.Usually the crystalline aluminum phosphate and its related compounds are prepared by maintaining the resulting solution or gel under the appropriate conditions mentioned above for a period of time to achieve its proper structure. It may be manufactured by forming.
好ましくは、本発明に従う方法は１８時間と１４４時間
、特に２４時間と９６時間に亘る時間で実施される。Preferably, the process according to the invention is carried out over a period of 18 and 144 hours, especially between 24 and 96 hours.
適したアルミニウム給源の例は酸化アルミニウム、例え
ばギブサイト、ベーマイト、偽ベーマイトおよびアルミ
ニウムアルコキシド例えばイソプロポキシアルミニウム
の如きである。Examples of suitable aluminum sources are aluminum oxides such as gibbsite, boehmite, pseudoboehmite and aluminum alkoxides such as isopropoxyaluminum.
更に種々のアルミニウム給源の混合物もまた適切に適用
できる。特に好ましいアルミニウム給源はベーマイト（
ｂｏｅｈｍｉ ｔｅ）である。Furthermore, mixtures of different aluminum sources can also be suitably applied. A particularly preferred aluminum source is boehmite (
boehmite).
適したリン給源はリン酸およびその誘導体例えばエステ
ル、酸化リン、リン酸塩および亜リン酸塩、好ましくは
オルト−リン酸を含む０種々のリン給源の混合物も適用
できる。Suitable phosphorus sources include phosphoric acid and its derivatives such as esters, phosphorus oxides, phosphates and phosphites, preferably ortho-phosphoric acid. Mixtures of different phosphorus sources can also be applied.
Ｘの適した給源の例は適した塩化物、沃化物、臭化物、
硝酸塩、硫酸塩および酢酸塩、好ましくは酢酸塩そして
酸化物である。Examples of suitable sources of X are suitable chlorides, iodides, bromides,
Nitrates, sulphates and acetates, preferably acetates and oxides.
望むならば、製造された結晶性リン酸アルミニウムおよ
びその関連化合物は乾燥後方塊でき、カ焼された、実質
的にＲを有しないリン酸アルミニウムまたはその関連化
合物を生成できる。If desired, the crystalline aluminum phosphate and related compounds produced can be dried and then agglomerated to produce a calcined, substantially R-free aluminum phosphate or related compounds.
攪拌を行うことにより生成溶液またはゲルから都合良く
所望の結晶性リン酸アルミニウムまたはその関連化合物
を生成できることが判った。It has been found that the desired crystalline aluminum phosphate or related compounds can be conveniently produced from the resulting solution or gel by stirring.
光凱圓立■
本発明に従う新規な結晶性リン酸アルミニウムおよびそ
の関連化合物は分子篩、触媒または種々の接触反応の実
施に際しての触媒担体として適切に使用できる。The novel crystalline aluminum phosphate and its related compounds according to the present invention can be suitably used as molecular sieves, catalysts or catalyst supports in carrying out various catalytic reactions.
若し望むならば１またはそれ以上の（接触的に）活性物
、特にプロトンおよび／またはその前駆体および／また
は１またはそれ以上の第■族の金属（またはその化合物
）および／または遷移金属および／または稀土類金属お
よび／またはその前駆体が本発明の結晶性リン酸アルミ
ニウムおよびその関連化合物中に混入できる。これらは
例えば含浸やイオン交換のような公知技術により混入で
きる。If desired, one or more (catalytically) active substances, in particular protons and/or precursors thereof and/or one or more Group I metals (or compounds thereof) and/or transition metals and Rare earth metals and/or their precursors can be incorporated into the crystalline aluminum phosphate and related compounds of the present invention. These can be incorporated by known techniques such as impregnation or ion exchange.
実施例 本発明は下記実施例によりより詳述されよう。Example The invention will be explained in more detail by the following examples.
１隻■↓
５Ｃ３−１４として参照される、結晶性ＡＩ！、Ｐ０４
が、ベーマイト１３．７５ ｇ、８５％Ｈ，Ｐ ０４２
３、１ ｇ、２．２′−ビピリジル（ｂｉｐｙ） １５
．６ｇ、および水６８．６ ｇを混合してモル基準でＩ
Ａ２□Ｏｓ ： Ｉ ＰｔＯｓ ： １ ｂｔｐ
ｙ ： ４５Ｈ２Ｏの反応ゲル混合物を生じることに
より製造された。1 ship■↓ Crystalline AI referred to as 5C3-14! ,P04
However, 13.75 g of boehmite, 85% H, P 042
3.1 g, 2.2'-bipyridyl (bipy) 15
．． 6 g, and 68.6 g of water to make I on a molar basis.
A2□Os: I PtOs: 1 btp
y: prepared by producing a reaction gel mixture of 45H2O.
この混合物は７２時間１６０°Ｃで保たれ結晶性化合物
を得た。This mixture was kept at 160°C for 72 hours to obtain a crystalline compound.
この合成後、この生成結晶性化合物は濾過により反応混
合物から分離され、水洗されて１２０°Ｃで乾燥された
。After this synthesis, the resulting crystalline compound was separated from the reaction mixture by filtration, washed with water and dried at 120°C.
得られた結晶性化合物は無水形で下記化学組成を有した
：
０、１３ Ｒ（Ａｆｆｉｏ、ｓＰｏ、５）Ｏｔ （こ
こにＲは２゜２′−ビピリジルから誘導された化合物を
表す）。The crystalline compound obtained had the following chemical composition in anhydrous form: 0,13 R (Affio, sPo, 5) Ot (where R represents a compound derived from 2°2'-bipyridyl).
この組成は下表２に与えた分析線を少なくとも含有する
Ｘ線回折パタンを有した。This composition had an X-ray diffraction pattern containing at least the analytical lines given in Table 2 below.
表２
実ｍ
結晶性５ＡＰＯ，が、ベーマイト３．４ｇ、８５％Ｈｓ
ＰＯ４５，２ｇ、２．２’−ビピリジル（ｂｉｐｙ）３
．９ｇ、シリカゾル（Ｌｕｄｏｘ＋ ｓ、ａ、） １
．２ ｇおよび水２１．４ｇを混合し、モル基準で０．
３ＳｉＯ，：ＩＡｊ！ｇｏ３ ： ０．９Ｐ２Ｏｓ
： １ ｂｉｐｙ ： ５６ＨｚＯを有する反応ゲル
混合物を生成して製造された。Table 2 Actual crystalline 5APO, boehmite 3.4g, 85% Hs
PO45.2g, 2.2'-bipyridyl (bipy)3
．． 9g, silica sol (Ludox+ s, a,) 1
．． 2 g and 21.4 g of water were mixed, and on a molar basis 0.2 g and 21.4 g of water were mixed.
3SiO,:IAj! go3: 0.9P2Os
: 1 bipy : produced a reaction gel mixture with 56 HzO.
この混合物は７２時間１６０°Ｃで保たれ結晶性化合物
を得た。This mixture was kept at 160°C for 72 hours to obtain a crystalline compound.
この合成後、この生成結晶性化合物は濾過により反応混
合物から分離され、水洗されて１２０°Ｃで乾燥された
。After this synthesis, the resulting crystalline compound was separated from the reaction mixture by filtration, washed with water and dried at 120°C.
得られた結晶性化合物は無水形で下記化学組成を有した
：
０、１２ Ｒ（Ｓ ｔａ、ａｔＡｌ、、ａｑＰｏ、ａｍ
）Ｏｘ （ここにＲは２．２′−ビピリジルから誘導さ
れた化合物を表す）、この組成は表２に与えた分析線を
少なくとも含有するＸ線回折バタンを有した。The crystalline compound obtained had the following chemical composition in anhydrous form: 0,12R(Sta,atAl,,aqPo,am
) Ox (where R represents a compound derived from 2,2'-bipyridyl), this composition had an X-ray diffraction pattern containing at least the analytical lines given in Table 2.
１施■ユ
結晶性ＣｏＡｊ！ＰＯ，が、ベーマイト３．１ｇ、８５
％ＨｓＰＯａ ５．８ｇ、２．２’−ビピリジル（ｂｉ
ｐｙ） ３．９ ｇ、Ｃ０（ＣＨｓＣＯＯ）ｔ４ Ｈ
ｇ０ ２゜２ｇおよび水１９．２ ｇを混合しモル基準
で０．３Ｃｏ０ ： ０．９ＡｌｚＯｚ ： Ｉ Ｐ
ｘＯｓ ： １ ｂｉｐｙ ： ５０．５Ｈ１Ｏの反
応ゲル混合物を生成して製造された。1st ■ Yu crystalline CoAj! PO, is boehmite 3.1g, 85
%HsPOa 5.8g, 2.2'-bipyridyl (bi
py) 3.9 g, C0(CHsCOO)t4H
Mix 2゜2 g of g0 and 19.2 g of water to obtain 0.3Co0: 0.9AlzOz: I P on a molar basis.
xOs: 1 bipy: 50.5H1O reaction gel mixture was produced.
この混合物は７２時間１６０″Ｃで保たれ結晶性化合物
を得た。This mixture was kept at 160''C for 72 hours to obtain a crystalline compound.
この合成後、この生成結晶性化合物は濾過により反応混
合物から分離され、水洗されて１２０°Ｃで乾燥された
。After this synthesis, the resulting crystalline compound was separated from the reaction mixture by filtration, washed with water and dried at 120°C.
得られた結晶性化合物は無水形で下記化学組成を有した
：
０、１２ Ｒ（ＣＯｅ、ｏ４Ａｊ！ａ、４．Ｐｅ、ａｗ
）Ｏｓ （ここにＲは２．２′−ビピリジルから誘導さ
れた化合物を表す）、この組成は表２に与えた分析線を
少なくとも含有するＸ線回折パタンを有した。The crystalline compound obtained had the following chemical composition in anhydrous form: 0,12R(COe, o4Aj!a, 4.Pe, aw
) Os (where R represents a compound derived from 2,2'-bipyridyl), this composition had an X-ray diffraction pattern containing at least the analytical lines given in Table 2.
発明の概要
本発明は合成無水形として化学組成ｍＲ（Ｘ、Ａｆｆｉ
、Ｐ ｘ） Ｏ□であって、ここにＲは２．２′−ビ
ピリジル（ビピリジン）部分であり、χは／ｌおよび／
またはＰに代替できる１またはそれ以上の元素を表し、
ｍ＝０．０１−０．３３、
ｎ＝０−０．４０、
ｑ ＝ ０．３０−０．６０、
ｘ ＝ ０．３０−０．６０および
ｎ＋ｑ＋ｘ＝１である組成を有する結晶性リン酸アルミ
ニウムおよび関連化合物に関し更にかかる化合物はアル
ミニウム源、リン源、任意的には少な（とも−個のＸ成
分源および２．２′−ビピリジル部分に基づいた型給源
を含む生成溶液またはゲルを形成し、この混合物を結晶
性リン酸アルミニウムまたはその関連化合物を生成する
に充分な時間上昇温度で保ち、次いで得られた結晶性生
成物を分離し乾燥し次いでカ焼する方法により製造され
る。SUMMARY OF THE INVENTION The present invention provides chemical composition mR(X, Affi) as a synthetic anhydrous form.
, P x) O□, where R is the 2,2'-bipyridyl (bipyridine) moiety and χ
or represents one or more elements that can be substituted for P, m = 0.01-0.33, n = 0-0.40, q = 0.30-0.60, x = 0.30-0. 60 and n + q + forming a product solution or gel containing a type source based on It is manufactured by drying and then calcining.
Claims (21)
Ｐ＿ｘ）Ｏ＿２であって、ここにＲは２，２′−ビピリ
ジル（ビピリジン）部分であり、ＸはＡｌおよび／また
はＰに代替できる１またはそれ以上の元素を表し、 ｍ＝０．０１−０．３３、 ｎ＝０−０．４０、 ｑ＝０．３０−０．６０、 ｘ＝０．３０−０．６０および ｎ＋ｑ＋ｘ＝１である組成を有し、そして少なくとも下
記の分析線を含有するＸ線回折パタンを有する結晶性リ
ン酸アルミニウムおよびその関連化合物： ▲数式、化学式、表等があります▼(1) Chemical composition mR (X_nAl_q
P_x)O_2, where R is a 2,2'-bipyridyl (bipyridine) moiety, X represents one or more elements that can be substituted for Al and/or P, and m=0.01-0 .33, n=0-0.40, q=0.30-0.60, x=0.30-0.60 and n+q+x=1, and contains at least the following analytical lines: Crystalline aluminum phosphate and related compounds with X-ray diffraction patterns: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼
その関連化合物において、 ｍ＝０．１０−０．２０、 ｎ＝０−０．３０、 ｑ＝０．４４−０．６０および ｘ＝０．４４−０．６０である化合物。(2) In the crystalline aluminum phosphate and its related compounds according to claim 1, m=0.10-0.20, n=0-0.30, q=0.44-0.60 and x=0. 44-0.60.
ルミニウムおよびその関連化合物において、Ｒは１また
はそれ以上のアルキル基、好ましくは炭素原子６個より
多くないアルキル基、特にメチル、エチルおよび／また
はプロピル基を含有する２，２′−ビピリジル部分から
誘導される上記化合物。(3) In crystalline aluminum phosphate and related compounds according to any of claims 1 or 2, R is one or more alkyl groups, preferably not more than 6 carbon atoms, especially methyl, ethyl and / or the above compounds derived from a 2,2'-bipyridyl moiety containing a propyl group.
ミニウムおよびその関連化合物で、Ｒが２個の同様に置
換されたピリジル基から構成される２，２′−ビピリジ
ル部分から誘導される上記化合物。(4) Crystalline aluminum phosphate and its related compounds according to any one of claims 1 to 3, wherein R is derived from a 2,2'-bipyridyl moiety composed of two similarly substituted pyridyl groups. The above compound.
その関連化合物であって、Ｒが４，４′−ジメチル２，
２′−ビピリジルから誘導される化合物。(5) Crystalline aluminum phosphate and its related compounds according to claim 4, wherein R is 4,4'-dimethyl 2,
Compounds derived from 2'-bipyridyl.
その関連化合物であって、Ｒが２，２′−ビピリジルか
ら誘導される化合物。(6) Crystalline aluminum phosphate and its related compounds according to claim 1, wherein R is derived from 2,2'-bipyridyl.
ミニウムおよびその関連化合物であって、元素Ｘが１ま
たはそれ以上のベリリウム、マグネシウム、チタン、マ
ンガン、鉄、コバルト、亜鉛、バナジウム、ニッケル、
クローム、ケイ素、リチウム、ホウ素、ガリウム、ゲル
マニウムおよび砒素を表し、好ましくは１またはそれ以
上のマグネシウム、マンガン、チタン、鉄、コバルトお
よびケイ素を表す化合物。(7) Crystalline aluminum phosphate and its related compounds according to any one of claims 1 to 6, wherein the element X is one or more of beryllium, magnesium, titanium, manganese, iron, cobalt, zinc, vanadium, and nickel. ,
Compounds representing chromium, silicon, lithium, boron, gallium, germanium and arsenic, preferably one or more of magnesium, manganese, titanium, iron, cobalt and silicon.
ミニウムおよびその関連化合物において、１またはそれ
以上の（接触的に）活性物が混合されており、好ましく
はプロトンおよび／またはその前駆体および／または１
またはそれ以上の第III族の金属（またはその化合物）
および／または遷移金属および／または希土類金属およ
び／またはその前駆体である上記化合物。(8) In the crystalline aluminum phosphate and related compounds according to any of claims 1 to 7, one or more active substances are mixed (catalytically), preferably protons and/or precursors thereof. and/or 1
or more Group III metals (or compounds thereof)
and/or the above compounds which are transition metals and/or rare earth metals and/or precursors thereof.
はその関連化合物を、アルミニウム源、リン源、任意的
には少なくとも一個のＸ成分給源および２，２′−ビピ
リジル部分に基づいた型給源を含む生成溶液またはゲル
から製造する方法において、この混合物を結晶性リン酸
アルミニウムまたはその関連化合物を生成するに充分な
時間上昇温度で保ち、次いで得られた結晶性生成物を分
離し乾燥し、上記溶液またはゲル内で上記種々の成分が
当初から下記のモル比で存在する方法：Ｒ：Ａｌ＿２Ｏ
＿３＝０．１−３ Ｘ：Ａｌ＿２Ｏ＿３＝０−２ ｐ：Ａｌ＿２Ｏ＿３＝０．３−１．３ Ｈ＿２Ｏ：Ａｌ＿２Ｏ＿３＝４０−５００(9) The crystalline aluminum phosphate or its related compound according to claim 1 is combined with an aluminum source, a phosphorus source, optionally at least one X component source and a type source based on a 2,2'-bipyridyl moiety. in which the mixture is held at an elevated temperature for a sufficient period of time to form crystalline aluminum phosphate or related compounds, and the resulting crystalline product is then separated and dried and A method in which the various components described above are initially present in the following molar ratios in a solution or gel: R: Al_2O
_3=0.1-3 X: Al_2O_3=0-2 p: Al_2O_3=0.3-1.3 H_2O: Al_2O_3=40-500
はゲル中の種々の成分は当初から下記のモル比で存在す
る方法： Ｒ：Ａｌ＿２Ｏ＿３＝０．１５−２ Ｘ：Ａｌ＿２Ｏ＿３＝０−２ Ｐ：Ａｌ＿２Ｏ＿３＝０．４−１．２５ Ｈ＿２Ｏ：Ａｌ＿２Ｏ＿３＝４５−３２０(10) A method according to claim 9, in which the various components in the product solution or gel are initially present in the following molar ratios: R: Al_2O_3 = 0.15-2 X: Al_2O_3 = 0-2 P: Al_2O_3=0.4-1.25 H_2O: Al_2O_3=45-320
ミニウム源として酸化アルミニウムおよび／またはその
誘導体、好ましくはベーマイト（ｂｏｅｈｍｉｔｅ）を
使用する方法。(11) A method according to claim 9 or 10, in which aluminum oxide and/or its derivatives, preferably boehmite, are used as the aluminum source.
て、リン酸類、酸化リン類、リン酸塩または亜リン酸塩
類を、リン給源として使用する方法。(12) The method according to any one of claims 9 to 11, wherein phosphoric acids, phosphorus oxides, phosphates, or phosphites are used as a phosphorus source.
、１またはそれ以上のアルキル基、好ましくは炭素原子
６個より多くなく含有するアルキル基、特にメチル、エ
チルおよび／またはプロピル基を含有する２，２′−ビ
ピリジル部分に基づいた型給源を使用する上記方法。(13) A method according to any of claims 9 to 12, comprising one or more alkyl groups, preferably containing no more than 6 carbon atoms, in particular methyl, ethyl and/or propyl groups. , 2'-bipyridyl moiety.
に置換したピリジル基からなる２，２′−ビピリジル部
分に基づいた型給源を使用する上記方法。14. The method of claim 13, using a mold source based on a 2,2'-bipyridyl moiety consisting of two similarly substituted pyridyl groups.
４，４′−ジメチル２，２′−ビピリジルを使用する方
法。(15) A method according to claim 14, in which 4,4'-dimethyl 2,2'-bipyridyl is used as a mold source.
，２′−ビピリジルを使用する方法。(16) In the method according to claim 9, two
, 2'-bipyridyl.
、成分Ｘを適当な塩化物、ヨウ化物、臭化物、硫酸塩、
硝酸塩、酢酸塩または酸化物の形態で使用する方法。(17) In the method according to any one of claims 9 to 16, component
Method of use in nitrate, acetate or oxide form.
、温度を８０℃と２２０℃間に保ち、特に１００℃と２
００℃間に保つ方法。(18) The method according to any of claims 9 to 17, wherein the temperature is maintained between 80°C and 220°C, in particular between 100°C and 220°C.
How to maintain temperature between 00℃.
、該生成溶液またはゲルを結晶形成条件下１８時間と１
４４時間に亘る時間保持する方法。(19) The method according to any one of claims 9 to 18, wherein the product solution or gel is heated under crystal-forming conditions for 18 hours and 1 hour.
How to hold for 44 hours.
、得られた結晶性生成物をカ焼する方法。(20) A method according to any one of claims 9 to 19, in which the obtained crystalline product is calcined.
れかに記載の結晶性リン酸アルミニウムまたはその関連
化合物を使用する方法。(21) A method of using the crystalline aluminum phosphate or its related compound according to any one of claims 1 to 8 when carrying out a catalytic reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898920906A GB8920906D0 (en) | 1989-09-15 | 1989-09-15 | Novel crystalline aluminophosphates and related compounds |
| GB8920906.8 | 1989-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03112803A true JPH03112803A (en) | 1991-05-14 |
Family
ID=10663126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2241346A Pending JPH03112803A (en) | 1989-09-15 | 1990-09-13 | Novel crystalline aluminum phosphate and its related compounds |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5035870A (en) |
| EP (1) | EP0417863B1 (en) |
| JP (1) | JPH03112803A (en) |
| CA (1) | CA2025333A1 (en) |
| DE (1) | DE69018548T2 (en) |
| DK (1) | DK0417863T3 (en) |
| ES (1) | ES2071747T3 (en) |
| GB (1) | GB8920906D0 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2676183B1 (en) * | 1991-05-06 | 1994-09-30 | Inst Francais Du Petrole | CATALYST FOR CATALYTIC CRACKING OF HYDROCARBON CHARGES COMPRISING A SUBSTITUTED GALLIUM PHOSPHATE. |
| FR2676233B1 (en) * | 1991-05-06 | 1995-07-21 | Inst Francais Du Petrole | USE, IN A HYDROCRACKING PROCESS OF A HYDROCARBON CHARGE, OF A CATALYST COMPRISING A SUBSTITUTED GALLIUM PHOSPHATE. |
| DE4131268A1 (en) * | 1991-09-20 | 1993-03-25 | Basf Ag | METHOD FOR PRODUCING ALUMO AND SILICOALUMOPHOSPHATES WITH AEL STRUCTURE USING 1,2-BIS (4-PYRIDYL) ETHANE |
| NO310106B1 (en) * | 1996-03-13 | 2001-05-21 | Norsk Hydro As | Microporous, crystalline metallophosphate compounds, a process for the preparation and use thereof |
| DE60141057D1 (en) * | 2000-04-06 | 2010-03-04 | Dalian Chemical Physics Inst | molecular sieves |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4310440A (en) * | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
-
1989
- 1989-09-15 GB GB898920906A patent/GB8920906D0/en active Pending
-
1990
- 1990-05-15 US US07/523,513 patent/US5035870A/en not_active Expired - Lifetime
- 1990-09-10 EP EP90202413A patent/EP0417863B1/en not_active Expired - Lifetime
- 1990-09-10 DK DK90202413.2T patent/DK0417863T3/en active
- 1990-09-10 DE DE69018548T patent/DE69018548T2/en not_active Expired - Fee Related
- 1990-09-10 ES ES90202413T patent/ES2071747T3/en not_active Expired - Lifetime
- 1990-09-13 CA CA002025333A patent/CA2025333A1/en not_active Abandoned
- 1990-09-13 JP JP2241346A patent/JPH03112803A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE69018548D1 (en) | 1995-05-18 |
| ES2071747T3 (en) | 1995-07-01 |
| CA2025333A1 (en) | 1991-03-16 |
| DE69018548T2 (en) | 1995-10-05 |
| EP0417863B1 (en) | 1995-04-12 |
| GB8920906D0 (en) | 1989-11-01 |
| DK0417863T3 (en) | 1995-05-08 |
| EP0417863A3 (en) | 1992-01-22 |
| US5035870A (en) | 1991-07-30 |
| EP0417863A2 (en) | 1991-03-20 |
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